2-aminothiophene azo compounds



Patented Mar. 18, 1958 Z-AIVHNQTHIOPIENE AZO COMPOUNDS Edmund B. Towne, William H. Moore, and Joseph B. Dickey, Kingsport, Tenn, assignors to Eastman Kodak (Iornpany, Rochester, N. Y., a corporation of New Jersey No Drawing. Application August 12, 1955 Serial No. 528,133

12 Claims. ((11. 260-154) This invention relates to new Z-aminothiophene azo compounds, to the application of the new azo compounds to the art of dyeing or coloring and to materials colored with the new azo compounds of the invention.

We have discovered that the new monoazo compounds having the formula:

wherein X represents a nitro group or an alkylsulfonyl group having 1 to 4, inclusive, carbon atoms, Y represents an alkyl-sulfonyl group having 1 to 4, inclusive, carbon atoms or a sulfonealkylamido group having 1 to 4, inclusive, carbon atoms and Q represents the radical of a -pyrazolone compound joined to the azo bond shown through the carbon atom in its 4-position, the radical of barbituric acid, the radical of 2-iminobarbituric acid, the radical of 4-iminobarbituric acid, the radical of Z-imino-B-cyanobarbituric acid, the radical of thiobarbituric acid or the radical of 4-iminothiobarbituric acid are useful for coloring a considerable number of different textile materials. They are useful, for example, for coloring textile materials made of or containing a cellulose alkyl carboxylic acid ester having 2 to 4 carbon atoms in the acid groups thereof, sulfone polyester textile materials, nylon textile materials, wool, polyethylene terephthalate (Dacron) textile materials and poiyacrylonitrile, especially acrylonitrile graft polymer, textile materials.

Ordinarily the azo compounds of our invention are applied by known dyeing techniques to fabrics or fibers made of the aforesaid textile materials. However, coloration can also be efiected, for example, by incorpo rating the azo compounds into the spinning dope in accordance with known techniques and spinning the fiber as usual. The azo compounds of our invention have varying utility as dyes. The degree of utility varies, for example, depending upon the material being colored and the formula of the azo compound.

By cellulose alkyl carboxylic acid esters having two to four carbon atoms in the acid groups thereof, We mean to include, for example, both hydrolyzed and unhydrolyzed cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate-propionate and cellulose acetate-butyrate.

The new monoazo'compounds of our invention are prepared by diazotizing a 2-aminothiophene compound having the formula:

(II) HC---O-X ll ll Y-C -NH2 wherein X represents a nitro group or an alkylsulfonyl group having 1 to 4, inclusive, carbon atoms and Y represents an alkylsulfonyl group having 1 to 4, inclusive, carbon atoms or a sulfonalkylamido group having 1 to hi 4, inclusive, carbon atoms and coupling the diazonium compound obtained with a S-pyrazolone compound, barbituric acid, Z-iminobarbituric acid, 4-iminobarbituric acid, 2-imino-3-cyanobarbituric acid, thiobarbituric acid and 4-iminothiobarbiturie acid.

The monoazo compounds of our invention yield yellow, orange and orange-red shades on the textile materials indicated hereinbefore which have good fastness to light, washing and sublimation, excellent gas fastness and which discharge to a pure white.

While our invention relates broadly to the new monoazo compounds having the formula numbered I insofar as those azo compounds which contain a 5-pyrazolone nucleus are concerned, it relates more particularly to the thiophene azo pyrazolone compounds having the formula:

(III) wherein R represents a hydrogen atom or a phenyl radical, R represents a methyl group, a carboxyl group, a carbomethoxy group, a carboethoxy group, a phenyl group or a tritluoromethyl group and X and Y have the meaning previously assigned to them.

The Z-aminothiophene compounds used in the preparation of the new azo compounds of our invention are nev. compounds. They are described and claimed in our copending application Serial No. 528,132, filed August 12, 1955.

2 amino 3,5 bis(methylsulfonyl) thiopheue, 2 amino 3,5 bis (ethylsulfonyl) thiophene, 2 amino- 3,5-bis (n-propylsulfonyl -thiophene, 2-amino-3,5-bis (isopropylsulfonyl) thiophene, 2 amino 3,5 bis(nbutylsulfonyl) thiophene, 2 amino 3 nitro 5- methylsulfonyithiophene, 2-amin'o-3-nitro-5-ethylsulfonyl thiophene, 2-amino-3-nitro-5-n-propylsulfonylthiophene, 2 amino 3 nitro 5 n butysulfonylthiophene, 2 amino 3 nitro 5 sulfonemethylamidothiophene, 2-amino3-nitro-5-sulfonethylamidothiophene, 2-amino-3- nitro-5-sulfone-n-propylamidothiophene and 2-amino-3- nitro-5-sulfone-n-butylamidothiophene are illustrative of the Z-aminothiophene compounds used in the preparation of the azo compounds of our invention.

3-methyl-5-pyrazolone, S-carboxy-S-pyrazolone, 3-carbomethoxy-S-pyrazolone, 3-carboethoxy-S-pyrazolone, 3- arnino-S-pyrazolone, 3-hydroxy-5-pyrazolone, 3-trifluoromethyl-5-pyrazolone, l-phenyl-3-methyl-S-pyrazolone, l phenyl-3-amino-5-pyrazolone, 1-phenyl-3-hydroxy-5-pyrazolone, 1-phenyl-3-methyl-5-p-nitrophenyl pyrazolone, 3- phenyl-S-pyrazolone, 1-phenyl-3-carbomethoxy-5-pyrazolone, 1-phenyl-3-carboethoxy-S-pyrazolone, l-p-nitrophenyl-3-methyl-5-pyrazolone, 1-o-nitrophenyl-3-methyl- S-pyrazolone, l-p-methylphenyl-3-methyl-5-pyrazolone, 1- p methoxyphenyl 3 amino 5 pyrazolone, 1 prnethylphenyl-3-amino-5-pyrazolone, 1-o-chloro-phenyl-3- amino-S-pyrazolone, 1-p-chlorophenyl-3-amino-5-pyrazol one,l-p-ethylphenyl-3-methyl-5-pyrazolone and l-p-chlorophenyl-3-methyl-5-pyrazolone, for example, are illustrative of the pyrazolone compounds used in the preparation of the azo compounds of our invention.

The monoazo compounds of our invention are dyes for fibers prepared from graft polymers obtained by graft polymerizing acrylonitrile alone or together with one or more other monoethylenic monomers with a preformed polymer. The preformed polymer can be a homopolymer (a polymer prepared by polymerization of a single monomer) or it can be an interpolymer such as a copolymer (a polymer prepared by the simultaneous polymerization in a single reaction mixture of two monomers) or -a terpolymer (apolymer prepared by the simultaneous polymerization in a single reaction mixture of three monomers), or the like, and the graft polymers for which the dyes 'are' particularly useful are those containing at least by wigh't' of combined acrylonitrilegrafted to V the preformed polymer molecule. a i

"The" graft polymers which can be dyed are thus polymers having directed placement of the p'olymerizedmonometric units in the graft polymer molecule as distinguished from the random distribution obtained in interpolyrner's which areprepared by simultaneous polymerization of all of the monomeric materials in the polymer. The preformed polymer can be either a homopolymer of any of the well-known'polymerizable monomers containing a':single--CH=C group and desirably a CH =C group; orian-interpolymerfoftwo or more of such monorners; and the -grafting can be effected with the preformed homo'p'olymer or interpolymr in the polymerization mixture in which it was formed (i. e. a live polymer) or with the preformed polymer isolated from the polymerizationmixture in which it was formed (i. e. a dead polymer).

The preformed polymer'desirably is a homopolymer of a vinyl pyridine, an acrylamide, a maleamide, a fumar-v amide, an acrylate, a methacrylamide, a methacrylate,

an itaconamide, a citraconarnide, a fumaramate, an itamonoethylenicmonomer, including any of the monomers enumerated hereinabove, with the preformed live or dead homopolyn er o r"interpolymer whereby the 'acrylonitrile alone 'ortogether with another grafting monomer iscom- 4 I aqueous sodium hydroxide was added at such a rate as to. maintain a pI-Lof 8-9. The temperature. of, the reaction mixture was maintained below C. by means of an ice bath. After about 1 hour the reaction slowed and the reaction mixture was then gradually heated to 70 C. while maintaining a pH of 8-9 by addition of 25% aqueous sodium hydroxide as needed. When the reaction; mixture,- containing the disodium salt of 2-acetamido-3,S-thiophenedisulfinic acid, reached the point that it could be stirred at 70 C. for 15 minutes with no-change in pH, it was neutralized with chloroacetic acid after which'0.5 grarn'of potassium iodide V were added and the reaction mixture heated 'to reflux;

' A neutral solutionof 10.25grams .of sodium chloroacetate in 20 cc. of water was added and the'reaction" mixture refluxed for 6 hours. The reaction mixture was then cooled and the 2acetamido-3,5-bis(niethylsulfonyD- thiophene which separated as a solid was collected on a reaction mixture was filtered'while hot and the filtrate bined with the preformed polymer molecule to give a V graft polymer containing from'5 to 95% by weight of combined'acrylonitrile.I j V Insofar as graft polymers are. concerned, the new azo compounds of 'our'invention are of particular utility for dyeing fibers preparedffrom a graft polymer obtainedby graft polymerizing. acrylonitrile'and an acrylamide or methacrylamide with a preformed copolymer of acrylonitrile and the sameior different acrylamide or methacrylamide/ U. s. Patent 2,620,324, issued December 2, 1952,.U. 5.

Patent 2,649,434, issued August 18, 1953, and U. S. Patent 2,657,191, issued October 27, 1953, disclose other typical graft polymers that can be dyed with the new 7 azo compounds of our invention.

Sulfonepolyester textilernaterials that can be colored with the new azo compounds of our'invention are dis closed in U. S. Patent 2,614,120, issued October 14, 1952. Additional sulfone polyester textile materials that can be colored with our new azo compounds are disclosed and claimed in copending Caldwell U. S. application Serial No. 313,061, filed October 3, 1952, .noWPatent EXAMPLE i i "6.76 grams of .2acetamido-3,5-bis(chlorosulfonyl)- p e'ne (moan, 615 9 51] and 5.8 grams of sodium sul fite were stirred together in 20 96- Q Wa hil? was chilled in an ice bath. The tan colored crystals of 2-amino-3,5-bis(methylsulfonyl)-thiophene which precipitated werecollectedon--a -filter and washed with Water until neutral.- -Ayield of 1.55 grams was obtained. a

After recrystallization' from water,- the 2-amir'1 o-3,5-bis- (methylsulfonyl) -thiophene' melted at. 201.4 C.

5.02 grams of alkalinesolution (pH 8-9) of the vdisodium salt of ;2-acetamido 3,S-thiophenedisirlfinic acid,

prepared according to theproceduredescribed in Exam pie 1, was heated at reflux for 12 hours with 31 grams-I of ethyl iodide andsufiicient. ethyl'alcohol' to render the hot solution homogeneous. Upon completion of'the refluxing the excess ethyl iodide and ethyl alcohol were distilled off-and the ;2 acetamido-3,5-bis(ethylsulfonyl)- thiophene which formed was recovered from the reaction mixture by extraction with ethyl ether. The ethyl ether extract was dried over. anhydrous sodium sulfate and the ethyl'ether evaporated.

The 2-acetamido-3,5-bis(ethylsulfonyl)-thiophene prepared as described above was hydrolyzed with 4 N hydrochloric acid in accordance with the-procedure de scribed in Example 1 to obtain' 2 grams'of 2-amino-3,5- bis(ethylsulfonyl) -thiophenel i EXAMPLE 3 7 ,By the use of 34 gramsiof n-propyl iodide in place of ethyl iodide in Example 2, 2-aniino-3,5-bis(n-propylsulfonyl) -thioph ene is obtained. V

' r EXAMPLE 4 2-amino-3,5-bis(n-butylsulfoiiyl) thiophene was pre: pared in accordance with the procedure described Example 2 except'th at 36.8 gramsof n-butyl iodide was used in place of ethyl iodide and the reaction mixture was heated at reflux for ls hoursinstead of 12 hours. A yield of'2.8 'grams'was'obtain'ed EXAMPLES r 21.7 grams of 5-chlorosulfonyl-2-chlorothiophene (Annalen, 532, 264 [1937]) and 13.9 grams ofsodiu'm'sulfite were stirred together. in. 100 cc. of water While, 25 aqueous sodium hydroxide was added at such a rate as to maintain a pH of 8-9. The temperature of the reaction mixture was kept under 30 C. by means of, an ice bath; After about l-hour, the reaction slowed and-the reaction mixture wasthen gradually heated to C. while maintaining a pH of 8-9 by addition of 25% aqueous sodium hydroxide as needed; uWhen' the reaction mixture, containing' the sodium salt of 2-chlorothiophene-5-sulfinic acid, reaches the point that it can be stirred at 70 C. for 15 minutes with no change 111 pH, it was neutralized with I I Cifdl'd'itiic 101d [appronlnrhiy gram) and 2 grams of potassium iodide were added. The reaction mixture was then heated to reflux and a solution of 13.1 grams of sodium chloroacetate and 2.64 grams of chloroacetic acid in 50 cc. of water was added dropwise over a period of 3 hours. After this addition was completed, refluxing was continued for 4 hours longer. The reaction mixture was allowed to cool following which the 2-chloro- S-methylsulfonylthiophene formed in the reaction was extracted with ethyl ether. The'ethyl ether extract was dried over anhydrous calcium sulfate (e. g. Drierite, an anhydrous calcium sulfate having a highly porous granular structure and a high atfinity for water) and the ether evaporated. Upon recrystallization from cyelohexane 12 grams of 2-chloro-5-methylsulfonylthiophene having a melting point of 72 C.75 C. were obtained.

58.95 grams of 2-chloro-5-methylsulfonylthiophene were added portionwise over a period of 1 and /2 hours to an ice-cooled mixture of concentrated sulfuric acid (specific gravity 1.84, 96%) and fuming nitric acid (specific gravity 1.5, 90%). About half way through the addition a white solid began to separate from the reaction mixture. After the addition of the 2-chloro-5- methylsulfonylthiophene was completed, the reaction mixture was stirred at ice bath temperature for 1 and /2 hours, then drowned in ice, filtered and the product recovered on the filter was washed with cool water until neutral. Upon recrystallizing the product from ethyl alcohol 68.4 grams of 2-chloro-3-nitro-5-methylsulfonylthiophene melting at 150 C.-152 C. were obtained.

24.15 grams of 2 chloro 3 nitro 5 methylsulfonylthiophene were dissolved in 750 cc. of absolute ethyl alcohol. The solution thus obtained was stirred at 70 C. while anhydrous ammonia was bubbled in for 2 hours at 70 C. The reaction mixture was concentrated to approximately one-third its volume and cooled. The red solid product which precipitated was recovered by filtration and recrystallized from water containing charcoal to obtain 9.5 grams of 2-amino-3-nitro-5-methylsulfonylthiophene melting at 187 C.189 C.

EXAMPLE 6 By the use of 34 grams of isopropyl iodide in place of ethyl iodide in Example 2,2-amino-3,5-bis(isopropy1 sulfonyl) thiophene is obtained.

EXAMPLE 7 An alkaline, aqueous ethyl alcohol solution (pH 8-9) of 20.5 grams of the sodium salt or" 2-chlorothiophene- 5-sulfinic acid prepared as described in the first part of Example 5 was heated at reflux for 12 hours with 83 grams of ethyl iodide. The excess ethyl iodide and ethyl alcohol were distilled oil" and the 2-chloro-5-ethylsulfonylthiophene formed by the reaction was separated from the reaction mixture by extraction with ethyl ether. The ethyl ether extract was dried and the ethyl ether distilled oil to yield 12.7 grams of 2-chloro-5-ethylsulfonylthiophene.

The 12.7 grams of 2-chloro-5-ethylsulfonylthiophene prepared as described above were nitrated by adding it portionwise over a period of 1 and /2 hours to a mixture of 15 grams of concentrated 96% sulfuric acid and 5.2 grams of 90% nitric acid, cooled in an ice bath. After addition of the Z-chloro-S-ethylsulfonylthiophene was complete, stirring was continued for 1 and /2 hours and then the reaction mixture was drowned on ice, filtered, and the product recovered on the filter was washed well with water and dried. 13.5 grams of 2-chloro-3-nitro-5- ethylsulfonylthiophene were recovered as a white crystalline solid.

The 13.5 grams of 2-chloro-3-nitro-5-ethylsulfonyl-, thiophene prepared as described above were dissolved in were 400 cc. of absolute ethyl alcohol and aniinated bling anhydrous ammonia into the reaction mixture for 2 hours while maintaining the reaction mixture at 70 C.

I I 1 I I and stirring. Then the reaction mixture was concentrated to one-third its volume and cooled. A reddish solid precipitated and was recovered by filtration. The reddish solid was recrystallized from water to obtain 6.4 grams of 2-arnino-3-nitro-5-ethylsulfonylthiophene.

EXAMPLE 8 By the use of 85 grams of n-propyl iodide in place of ethyl iodide in Example 7, 2-amino-3-nitro-5-n-propylsulfonylthiophene is obtained.

EXAMPLE 9 By the use of 92 grams of n-butyl iodide in place of ethyl iodide in Example 7, 2-amino-3-nitro-5-n-butylsulfonylthiophene is obtained.

EXAMPLE 10 24.8 grams of 2 chloro 3 nitro-S-chlorosulfonylthiophene '(JCS, 1948, page 25) were dissolved in cc. of acetone and the solution resulting was stirred at 0C.- C. while 36 grams of a 33% aqueous solution of ethylamine were added over a period of about 1 and /2 hours. After stirring for an additional half hour at 0 C., the reaction mixture was poured into 400 cc. of ice water. On standing, the oil whichseparated became solid. 17.8 grams of crude 2-ChlOI'D-S-HitI'O-S-SUIfOH-s. ethylamidothiophene were thus obtained by recovery of the solid from the ice water. Upon recrystallization from aqueous ethyl alcohol a purified product melting at 70 C.73 C. was obtained.

4 grams of purified 2-chloro-3-nitro-5-sulfonethylamidothiophene obtained as described above was refluxed for 1 hour with 14 cc. of concentrated aqueous ammonium hydroxide in 50 cc. of ethyl alcohol. After refiuxing was complete, the reaction mixture was concentrated to one-third its volume and the "ammonium chlo ride which precipitated was removed by filtration. Upon evaporation of the remaining solution to dryness 3.1 grams of 2-amino-3-nitro-5-sulfonethylamidothiophene were obtained as an oil which solidified on standing.

EXAMPLE 11 By the use of an equivalent amount of methylamine, n-propylamine and n-butylamine, respectively, for ethylamine in Example 10, 2-amino-3-nitro-5-sulfonemethylamidothiophene, 2 amino 3-nitro-5-sulfone-n-propyl- 'amidothiop'nene and 2-amino-3-nitro-5-sulfone-n-butylamidothiophene, respectively, are obtained.

EXAMPLE 12 Nitrosylsulfuric acid was prepared by adding 1.52 grams of sodium nitrite portionwise to 10 cc. of concentrated sulfuric acid, with stirring, and allowing the temperature to rise to C. The solution thus obtained was then cooled to 5 C. and a mixture consisting of 3 cc. of propicnic and 17 cc. of acetic acid was added dropwise, with stirring, while allowing the temperature to rise to 15 C. and then keeping it there during the addition of the acid mixture. The reaction mixture thus obtained was then cooled to 0 C.-5 C. and 5.61 grams of 2-amino-3,5-bis- (methylsulfonyl)-thiophene were added portionwise while stirring, after which a mixture of 3 cc. of propionic acid and 17 cc. of acetic acid was added while keeping the temperature of the reaction mixture at 0 C.5 C. The reaction mixture was then stirred at 0 C.5 C. for 2 hours and the excess sodium nitrite present was destroyed by adding 1 gram of urea. A clear diazonium solution of 2- amino-3,5-bis (methylsulfonyD-thiophene was obtained by the foregoing precedure.

10 cc. of the diazonium solution prepared as described in the preceding paragraph were added with stirring to a solution of 0.58 gram of thiobarbituric acid in about 10 cc. of an acetic-propiom'c acid mixture prepared as desicribed in thfe prec eding paragraph. The coupling reaction whichdajkesj place was allowed to proceed for 1 hour after'which the reaction mixture was neutralized withisodium carbonate and drowned in water. The precipitated .dye compound was recovered byfiltration,

washed well with water and dried. 1.1 grams of the dye compoundhaving the formula:

V O=G-NE were thus obtained. It dyes the textile materials named hereinbefore such: as cellulose acetate; nylon, wool, sulfone polyester, polyethylene terephthalate and acrylonitrile graft polymer textile materials, for example, yellow shades having good fastness to gas. The dyeing on cellulose acetate has fair light fastness. V

propionic acid in accordance with the procedure described 7 in Example 12 for the diazotization of 2-amino-3,5-bis- (methylsulfonyl)-thiophene. A clear diazoniurn solution was obtained. a

cc; of the diazonium solution prepared in the preceding paragraph were added to a solution of 0.51 gram of 3-carboxy-5-pyrazolone dissolved in dilute aqueous so dium hydroxide and cooled'to 0 C. The coupling reaction which takes place was allowed to proceedfor about 1 hour and then the reaction mixture was drowned in 200 cc. of Water withstirring. After the drowned reaction mixture had stood for about 1 hour, the dye compound which precipitated was recovered by filtration, washed with water until neutral and dried. 1.07 grams of a dye which colors celluloseacetate, wool, nylon, Dacron and acrylonitrile graft polymer textile materials orangered shades having good fastness to gas'were thus obtained.

. EXAMPLE V r 10 cc; of the diazonium solution prepared as described in Example- 14 were coupled with 0.52 gram of barbituric acid. Coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 12. The dye compound obtained colors the; textile materials disclosed herein orange shades.

EXAMPLE l6 5.02 grams of 2-amino-3-nitro-5-sulfonethylamidothiophene were diazotized with nitrosylsulfuric acid in aceticpropionic acid in accordance with the procedure described in Example 12 for the diazotization of 2-amino-3,5-bis- (methylsulfonyl)-thiophene. A clear diazonium solution was obtained. i

10 cc. of the diazonium solution prepared as described in the preceding paragraph were coupled with 0.7 gram 7 Coupling and recov-' cry of the dye compound formed were carried out inacof 1 phenyl-3-methyl-5-pyrazoliue.

ooi'dance with the general preceduredescribed in Example 12; The dyecompound obtained colors the textile materials disclosed herein yellow shades. 7 i

"ExA rLE 17 i acid Coupling and recovery ofthe dye compound formed were carried out in accordance with the general procedure described in Example 12. The dye compound obtained colors the textile materials disclosed herein yellow shades; t

' EXAMPLE 1s 10 cc. of the diazonium solution prepared as described in Example 12 werecoupled with 0.51 gram of .Z-imino:

barbituric acid. 7 Coupling and recovery of the dye come pound formed were carried out in accordance with the general procedure described in Example 12.. The dye compound obtained colors the textile materials disclosed herein yellow shades.

EXAMPLE 19 10 cc. of the diazonium solution prepared asdescribed in Example 12 were coupled with 0.63 gram of 4-iminothiobarbituric acid. Coupling and recovery of the dye.

compound formed were carried out in accordance with the generalprocedure described in Example 12. The dye compound obtained colors the textile materials disclosed herein yellow shades. a

EXAMPLE 20 EXAMPLE 21. 7 10 cc. of the diazonium solution prepared as described in Example 12 were coupled with 0.4 gram of 3-amino-5- pyrazolone. Coupling and recovery of the dye compound formed were carried out in accordance with'the general procedure described in Example 12. The dye compound obtained colors the textile materials disclosed herein yellow shades.

EXAMPLE 22 10 cc. of the diazonium compound prepared as described in Example 12 were coupled with 0.76 gram of l-phenyl- S-amino-S-pyrazolone. compound formed were carried out in accordance with the general procedure described in Example 12. The dye compound obtained colors the textile materials disclosed herein yellow shades.

EXAMPLE 23 5.66 grams of 2-amino-3,5-bis(ethylsulfonyl)-thiophene were diazotized with nitrosylsulfuric acid in aceticpropionic acid in accordance with the procedure. de-

scribed in Example 12 for the diazotization of Z-amino- 3.5 -bis (-methylsulfonyl) -tl1iophene. A clear 7 diazonium solution was obtained.

. 10 cc. of the diazonium solution prepared as described in the preceding paragraph were coupled with 0.58 gram of thiobarbituric acid. Coupling and recovery of the dye compound formed were carried out in accordance. with the general procedure described in Example 12. Thedye compound obtained colors the textile materials, disclosed herein yellow shades.

V V V EXAMPLE 24 V p 6.12 grams 7 of 2-amino-3,5-bis(n-butylsulfonyl)-thiophene were diazotized with nitrosylsulfuric acid inacetic propionic acid in accordance "with the procedure 7 described inExample l2-for the dia zoti zation of Z-amino- 3,5-bis(methylsi1lfonyl}-thiophene. solution was obtained."

10 cc. of the diazoniurn solution prepared as described 7 in the preceding paragraph were coupled With OJIgram of 1-phenyl-3-methyl-5-pyraaolone. covery' of the dye compound formed were carried outin accordance with the general pfocedurefdescribed;

Coupling and recovery of the dye A clear diazonium Coupling and: re- I Example 12 The dye compound obtained colors the textile materials disclosed herein yellow shades.

EXAMPLE 25 EXAMPLE 26 4.74 grams of 2-amino-3-nitro-5-sulfonemethylamidothiophene were diazotized with nitrosylsulfuric acid in acetic-propionic acid in accordance with the procedure de- 20 procedure indicated hereinbefore.

scribed in Example 12 for'the cliazotization of Z-amino- 3,5-bis(methylsulfonyl)-thiophene. A clear diazonium solution was obtained.

10 cc. of the diazonium solution prepared as described 5 in the preceding paragraph were coupled with 0.51 gram of B-carboxy-S-pyrazolone. Coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 12. The dye compound obtained colors the textile materials 10 disclosed herein orange shades.

The following tabulation further illustrates the azo compounds included within the scope of our invention together with the color they produce on cellulose acetate. The compounds indicated below are prepared by diazo- 15 tizing the amines listed under the heading Amine and coupling the diazonium compounds obtained with the compounds specified in the column entitled Coupling Component. The diazotization and coupling reactions may, for example, becarried out following the general The colors these azo compounds yield on the other materials disclosed herein is generally similar to the color they produce on cellulose acetate. I

Amine Coupling Component Color 2-amino-3,5-bis(methylsulfonyD-thiophene (1) 4-Iminobarbituric acid yellow.

Do (2) 3-methyl-5-pyrazolone yellowish orange. D0. (3) 3-trifluoromethyl-5-pyrazolone D0. D0. (4) B-carboxy-fi-pyrazolone Do. Do. (5) 3-carbomethoxy-fi-pyrazolone. Do. Do (6) 3-carboethoxy-5-pyrazolonc D0. D0 (7) l-phenyl-3-methyl-5-pyraz0lone Do. Do- (8) 1-pheny1-3-carboethoxy-5-pyrazolone Do. Do (9) l-phenylpyrazole-3,5-dione Do. Z-amino (1) barbituric acid yellow. D0 (2) 2-iminobarblturic acid Do. Do (3) 4-iminobarbituric acid D0. D0. (4) 4-iminothiobarbituric acid Do. Do. (5) 2-lmino-3-eyanobarbituric acid Do. Do (6) 3-carboxy-5-pyrazolone yellowish orange Do (7) S-phenyl-fi-pyrazolone Do. Do--. (8) 1-phenyl-3-methyl-5-pyrazolone Do. 2-amino-3,5-bis(n-propylsulfonyl)-th10phene (1) barbituric acid yellow. D0 (2) thiobarbituric acid Do. Do (3) 3-carboxy-5-pyrazo1one yellowish orange. Do (4) 3-phenyl-5-pyrazolone Do. Do (5) l-phenyl-{i-methyl-5-pyrazolone. Do. 2-amino-3,5-bis(isopropylsulfonyl)-thiophene (1) barbituric acid yellow. Do (2) thiobarbituric acid--. Do. Do (3) 3-carboxy-5-pyrazolone yellowish orange. Do (4) 3-phenyl-5-pyrazolone Do. Do (5) l-pheny1-3-methyl-5-pyrazolone. Do. 2-amino-3,5-bis(n-butylsnlfonyl)-thlophene- (1) barbituric acid yellow. D0 (2) thiobarbituric acid--. Do. Do (3) 3-carboxy-5-pyrazolone yellowish orange (4) 3-phenyl-5-pyrazolone Do. (5) l-phenyl-S-methyl-dpyrazolone. Do. (1) thiobarbituric acid yelloworange (2) 2-iminobarbituric acid Do. (3) 4-iminobarbituric acid Do. (4) 4-iminothiobarbituric acid. Do. (5) 2-imino-3-cyanobarbituric acid Do. (6) 3-methyl-5-pyrazoione orange-red (7) S-trifiuoromethyl-5-pyrazolone Do. (8) 3-carboxy-5-pyrazolone Do. (9) 3-cazboethoxy-5-pyrazolone Do. (10) 3-phenyl-5-py'razolone Do. (11) l-phenyl-B-methyl-5-pyrazolona Do. (12) 1-phenyl-3-carboethom-5-pyrazolone Do. (l3) 1-phenylpyraz0le-3,5-dione .r Do. (1) thiobarbituric acid yellow orange (2) 2-iminobarbituric acid Do. (3) 3-carboxy-5-pyrazolone orange-red (4) 3-phenyl-5-pyrazolone Do. (5) 1-phenyl-3-methyl-5-pyrazolone Do. (1) barbituric acid yelloworange (2) thiobarbituric acid Do.

orange-red Do. (5) 1-phenyl-3-methyl-5-pyrazolone-. Do. (1) barbiturlc acid yellowish orange. (2) thiobarbituric acid o. (3) 3-oarboxy-5-pyrazol0ne orange-red. (4) 3-phenyl-5-pyrazolone Do. Do (5) 1-phenyl-3-methyl-5-pyrazolone Do.

' Amine Coupling Component Color 2-ammo-3-nitro-5 sulfone-methylamidothiophene- (1) barbituric acid yellowish orange. (2) thiobarbituric acid--- Do. (3) 3-carboxy-5-pyrazolone orange. (4) 3-phenyl-5-pyrazoloneorange-red (5) 1-phenyl-3-methyl-5-pyrazolone Do. (1) barbituric acid yellowish orange (2) thiobarhituric acid Do. (3) 2-iminobarbituric acid. Do. (4) 4-iminobarbituric acid" Do. (5) 4-iminothioharbituric ac Do. (6) 2-imino-3-cyanobarbiturie Do. (7) 3-methy1-5-pyrazo1one orange-red (8) 3-trifluoromethyl-fi-pyrazolone orange. (9) 3-carbomethoxy-5-pyrazolone Do. (10) S-carboethoxy-5pyrazolone-.. Do. (11) 3-phenyl-5-pyrazolone orange-red (12) l-phenyl-3-carboethozry-5-pyrazolone Do. (13) 1-phenylpyrazole-3,5-oione Do. (1) barbituric acid yellowish phene. orange D (2) thiobarbituric acid Do.

(3) 3-carboxy-5-pyrazolone--- orange. E4) 3-phenyl-5-pyrazolone orange-red.

5) 1-phenyl-3-methyl-5-pyrazolone Do. (1) baribturlc acid. yellowish orange. (2) thiobarbituric acid Do. (3) B-carboxy-fi-pyrazolone.-. orange. (4) 3-phenyl-5-pyrazolone orange-red. (5) 1-phenyl-3-methyl-5-pyrazolone Do.

Preparczltion of acrylonitrilc graft polymer 3.0 g. of acrylonitrile and 7.0 g. of N-methyl methdodecyl mercaptan. The emulsion was heated at 60 C. I 7

until 94% or more of the monomers had copolymerized; This result is usually accomplished by heating for about 12 hours. The copolymer contained approximately by weight of acrylonitrile and"7 0% 'by weight of N- methyl methacrylamide. The mixture was then cooled to room temperature, 50 cc. of water added and the mixture agitated until a homogeneous solution of dope con taining 10% by weight of the copolymer resulted.

30.7 g. (3.07 g. of copolymer) of the above-prepared solution or dope of the copolymer were placed in a jacketed reactor provided with an agitator and heat exchanger. There were then added 10 g. of acrylonitrile,

ll4 cc. of water, 0.58 'g. of 85% phosphoric acid, 0.1g.

of potassium persulfate, 0.17 g. of potassiumrnetabisullite, 0.1 g. of tertiary tdodecyl mercaptan and 0.56 g. of a 30% solution in water of N-methyl mcthacrylamid e and the mixture heated, with stirring, to C.,and then 'allowed to level ofi at 37'39 C. After the heat of polymerization had been removed and when the conversion of the acrylonitrile to polymer had reached 96% or more, which is usually accomplished in a period of about '12. hours, the temperature was raised to 90 C. The mother liquor was removed by centrifuging the polymerization mixture, the polymer precipitate being reslurried twice with'water and centrifuged to a 70% moisture cake. The

cake was dried under vacuum at 80 C. in an agitated dryer. The over-all yield of modified polyacrylonitrile product was over 90%. g 7

powder, now ready for spinning, was stored in-a moisture After hammermilling, the dry proof container. v V

The acrylonitrile graft polymer prepared as above and containing about. 18% by Weight of N-methyl methacrylamide was soluble in N,N-dimethylformamide. Fibers spun'by extruding a solution of the polymer product in- 'N,l-l-dimethylformamide into a precipitating bath had a softening temperature of about 240 C., an extensibility of about 20-30 percent depending on the drafting and relaxing conditions, and showed excellent aflinity for dyes.

Preparation of sulfo'ne polyester polymer 7 One hundred g. p,p-'sulfonyldi henzoic acid ethyl ester and 40 g. 1,5-pentanediol wereplaced in a reaction-vessel equipped with'astirre'r, a' short distillation column, and

the distillation of ethyl alcohol ceased, and the tempera:

'ture was raised to,2802,85 C. where it was held for 20 minutes. A vacuum of 0.5 to 1.0 mm. was applied for 1 hour while the temperature was maintained at 35 280-285 C. 1 A colorless product having an inherent viscosity of 0.80-0.90 in, 60% phenol-40% tetrachlorethane solution was obtainedj Fibers pulled from the 7 melt ,and cold-drawn 400500% show a sticking temperature of 240-250 C. ihe product is also useful for 40 films and sheets. V

The monoazo compounds of our invention can be applied to cellulose alkyl carboxylic acid esters having 2 to 4 carbon atoms in the acid groups thereof, nylon, acrylo- 'iiitrile graft polymers, s'ulfone polyester and polyethylene terephthalate textile materials in the form of an aqueous dispersion'and are ordinarilyso applied. To illustrate,

- the dye compound is finely ground with a dispersing agent "such as sodium lignin sulfonate, Turkey red ,oil, soap, or

' an oleyl glyceryl sulfate and the resulting mixture is disi perse'd'iri water; The dye bath thus prepared is heated to "a temperature approximating 45 C. C. and the textile material to be dyed is immersed in the dye bath, fol- A lowing which the temperature is gradually raised to 80" 'C.+90 C. andtmaintained at this temperature until dye- 55 ing is complete, usually one-halflo two'hours. From lflftime to.time'throughbuhthedyeing operation, the ma- --terial isworkedto promote even dyeing. 'Upon comple- .Iftionl'of the dyeing operation, the textile material is re moved from the dye bath, washed with an aqueous soap f .solution,lrinsed well with-water and dried.

' :13 alnfisisassiqfss tai re acrylonitrile graft P mers. describedhereinbefore it is necessary to dye at the 'boil for anextended period of time. Instances may be encountered where the fiber is not satisfactorily colored e5 "by the dyeing procedurej just described. In these instances specialdyeing techniques, such as the use of pressure, for example, developedby the art for the coloration of materials difficult to color may be employed jjf widely 'yarjying amounts; of dye can be used in the dyeing operation? The amount of dye used can be, for

*- 7 The'following'example illustrates one satisfactory'way in whichth'fibfs of the acrylonitrile graft polymers example,-. /s' to 3% (by' weight) of that of the textile ma- 7 can be dyed using the azo compounds of our invention. 16 milligrams of dye are ground with an aqueous solution of sodium lignin sulfonate until well dispersed or alternately the dye can be dissolved in cc. of hot Cellosolve. The dispersion or solution, as the case may be, is then poured into 150 cc. of water to which a small amount of a surface-active agent such as Igepon T (C17H33.CO.N(CI'I3).C2H4SO3N3.) Nekal BX (sodium alkylnaphthalene-sulfonate) or Orvus (sodium lauryl sulfate-type) has been added. The dye bath is then brought to the desired temperature and 5 grams of well wet-out fibers of the graft polymer are added thereto. Dyeing is continued until the proper shade is reached. From time to time throughout the dyeing operation, the material is Worked to promote even dyeing.

Acrylonitrile graft polymers including those of the type specifically described hereinbefore are described and claimed in Coover U. S. application Serial No. 408,012, filed February 3, 1954.

We claim:

1. The azo compounds having the formula:

wherein X represents a member selected from the group consisting of a nitro group and an alkylsulfonyl group having 1 to 4, inclusive, carbon atoms, Y represents a member selected from the group consisting of an alkylsulfonyl group having 1 to 4, inclusive, carbon atoms and a sulfonealkylamido group having 1 to 4, inclusive, carbon atoms and Q represents a member selected from the group consisting of the radical of a 5-pyrazolone compound joined to the azo bond shown through the carbon atom in its 4-position, the radical of barbituric acid, the radical of Z-iminobarbituric acid, the radical of 4-iminobarbituric acid, the radical of 2-imino-3-cyanobarbituric acid, the radical of thiobarbituric acid and the radical of 4-iminothiobarbituric acid.

2. The azo compounds of claim 1 wherein Q represents the radical of a S-pyrazolone compound joined to the azo bond shown through the carbon atom in its 4- position.

3. The azo compounds of claim 1 wherein Q represents the radical of barbituric acid.

4. The azo compounds of claim 1 wherein Q represents the radical of Z-iminobarbituric acid.

5. The azo compounds of claim 1 wherein Q represents the radical of thiobarbituric acid.

6. The azo compounds of claim 1 wherein Q represents the radical of 4-iminothiobarbituric acid.

7. The azo compounds having the formula:

14 wherein X represents a member selected from the group consisting of a nitro group and an alkylsulfonyl group having 1 to 4, inclusive, carbon atoms, Y represents a member selected from the group consisting of an alkyl- 5 sulfonyl group having 1 to 4, inclusive, carbon atoms and a sullonealkylamido group having 1 to 4, inclusive, carbon atoms, R represents a member selected from the group consisting of a hydrogen atom and a phenyl radical and R represents a member selected from the group consisting of a methyl group, a carboxyl group, a carbomethoxy group, a carboethoxy group, a phenyl group and a trifluoromethyl group.

8. The azo compound having the formula:

O=O-NH Hfi--?{7SO2CH3 H C aO2SC /CN=N([] $=S S O=C-NH 9. The azo compound having the formula:

- 0=o-NH HfiC-NO2 H CHsOaS-C C-N=NC (13 0 s O=C-NH 10. The azo compound having the formula:

HC--CSO2CH3 II II E CHaOzS-C\ /C =N(|3 %J S O=C\ /N N H 11. The azo compound having the formula:

HC--CNO u n CHtOaS--C CN=N(l -(l]J-COOH S 0=C\ /N N H 12. The azo compound having the formula:

HC-C-N0a H II H H GaHtNOnS-C C-N= GC-CHJ I 5 S O=C\ References Cited in the file of this patent UNITED STATES PATENTS 2,313,738 Dickey et al. Mar. 16, 1943 2,323,315 Dickey et al. July 6, 1943 OTHER REFERENCES Hartough: Thiophene and Its Derivatives, 1952, page 2 .60 

1. THE AZO COMPOUNDS HAVING THE FORMULA: 